Patterning Contacts in Carbon Nanotube Devices

ABSTRACT

A method to fabricate a carbon nanotube (CNT)-based transistor includes providing a substrate having a CNT disposed over a surface; forming a protective electrically insulating layer over the CNT and forming a first multi-layer resist stack (MLRS) over the protective electrically insulating layer. The first MLRS includes a bottom layer, an intermediate layer and a top layer of resist. The method further includes patterning and selectively removing a portion of the first MLRS to define an opening for a gate stack while leaving the bottom layer; selectively removing a portion of the protective electrically insulating layer within the opening to expose a first portion of the CNT; forming the gate stack within the opening and upon the exposed first portion of the carbon nanotube, followed by formation of source and drain contacts also in accordance with the inventive method so as to expose second and third portions of the CNT.

CROSS-REFERENCE TO A RELATED PATENT APPLICATION

This patent application is a divisional application of copending U.S. patent application Ser. No. 13/270,648, filed Oct. 11, 2011, the disclosure of which is incorporated by reference herein in its entirety.

TECHNICAL FIELD

The exemplary embodiments of this invention relate generally to carbon nanotube-based electronic devices and, more specifically, relate to methods for processing carbon nanotube devices to form gate and source/drain electrical contacts in a carbon nanotube-based transistor.

BACKGROUND

As scaling for conventional CMOS integrated circuits approaches quantum mechanical limits, alternative nanostructures and materials have been investigated in the semiconductor industry. Of such nanostructures and materials, carbon nanotubes (CNTs) offer excellent intrinsic properties that are suitable for high performance nanoscale devices.

CNTs are allotropes of carbon that exhibit a cylindrical nanostructure and are members of the fullerene structural family. Their name is derived from their long, hollow structure having walls formed by one-atom-thick sheets of carbon, known as graphene.

CNTs can be used to construct electronic devices such as transistors as evidenced by, for example, commonly assigned US 2011/0127492 A1, “Field Effect Transistor Having Nanostructure Channel”, Josephine B. Chang, Michael A. Guillorn and Eric A. Joseph, and commonly assigned US 2011/0127493 A1, .“Self Aligned Carbide Source/Drain FET”, Cyril Cabral, Jr., Josephine B. Chang, Alfred Grill, Michael A. Guillorn, Christian Lavoie and Eugene J. O'Sullivan.

SUMMARY

In accordance with an aspect thereof the exemplary embodiments of this invention provide a method of forming a field effect transistor. The method comprises providing a substrate having a carbon nanotube disposed over a surface of the substrate; forming a protective electrically insulating layer over the carbon nanotube; and forming a first multi-layer resist stack over the protective electrically insulating layer. The first multi-layer resist stack comprises a bottom layer, an intermediate layer and a top layer of resist. The method further comprises patterning and selectively removing a portion of the first multi-layer resist stack to define an opening for a gate stack, where selectively removing also completely removes the intermediate layer and the top layer of resist leaving the bottom layer. The method further comprises selectively removing a portion of the protective electrically insulating layer within the opening to expose a first portion of the carbon nanotube; forming the gate stack within the opening and upon the exposed first portion of the carbon nanotube; forming a second multi-layered resist stack upon the bottom layer and upon the gate stack; patterning and selectively removing a portion of the second multi-layer resist stack to define an opening for a source contact and an opening for a drain contact; selectively removing a portion of the protective electrically insulating layer within the source contact opening and within the drain contact opening to expose a second portion of the carbon nanotube and a third portion of the carbon nanotube; and applying contact material within the source contact opening and within the drain contact opening and upon the exposed second and third portions of the carbon nanotube.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIGS. 1A-1M, collectively referred to as FIG. 1, illustrate a process flow suitable for fabricating a transistor in accordance with embodiments of this invention, where

FIG. 1A depicts a starting structure composed of a substrate, an insulating layer and a CNT disposed on the insulating layer;

FIG. 1B shows the starting structure of FIG. 1A after the deposition of a protective layer over the CNT followed by the deposition of a tri-layer resist stack;

FIG. 1C shows the structure of FIG. 1B after patterning of the resist layer to form an opening where a gate stack will be formed;

FIG. 1D shows the structure of FIG. 1C after patterning of the OPL;

FIG. 1E shows the structure of FIG. 1D after a portion of the protective layer is removed within the opening thereby exposing a portion of the CNT that will form the channel of the fabricated transistor;

FIG. 1E′ shows an alternative embodiment of the structure of FIG. 1D after the portion of the protective layer is removed within the opening thereby exposing the portion of the CNT that will form the channel of the fabricated transistor, as well as the selective removal of the underlying insulating layer for suspending the exposed portion of the CNT;

FIG. 1F shows the structure of FIG. 1E after formation of a gate stack;

FIG. 1G shows the structure of FIG. 1F after excess gate metal and gate dielectric materials are removed;

FIG. 1H shows the structure of FIG. 1G after a re-application of patterning layers including a layer of LTO or SiARC material and a layer of resist;

FIG. 1I shows the structure of FIG. 1H after a contact metal pattern is exposed in the resist layer as a shape that spans the gate stack;

FIG. 1J shows the structure of FIG. 1I after LTO or SiARC material applied in FIG. H is removed;

FIG. 1K shows the structure of FIG. 1J after the contact pattern is transferred into the OPL;

FIG. 1L shows the structure of FIG. 1K after the protective layer is removed within the contact portion, thereby again exposing the CNT; and

FIG. 1M shows the structure of FIG. 1L after source (S) and drain (D) contact material is deposited and the structure is planarized.

FIG. 2 is sectional view through the structure at the completion of the processing of FIG. 1M along a plane indicated as ‘2’ in FIG. 1M, where the sectional view is taken through the gate stack.

DETAILED DESCRIPTION

The exemplary and non-limiting embodiments of this invention are described with reference to the process flow depicted in FIGS. 1A-1M, collectively referred to as FIG. 1. In general, FIG. 1 presents an enlarged cross-sectional view of a substrate 10 having various layers disposed over a major surface thereof. The various layer thicknesses are not drawn to scale.

FIG. 1A depicts a starting structure composed of the substrate 10, an insulating layer 12 and a CNT 14 disposed on the insulating layer. The starting structure assumes that the CNT growth and placement has been achieved by any suitable technique known in the art, and that the substrate 10 with aligned and deposited nanostructures (e.g., CNTs) is available. In practice the can be a large number of CNTs 14 present. The ensuing description will focus on a process to fabricate a transistor device where a portion of the length of the CNT 14 functions as a channel that passes through a gate stack. It should be appreciated that in practice a number of transistor devices may be disposed in a serial fashion along the length of one CNT 14. It should also be appreciated that in practice a single transistor device can contain a plurality of CNTs 14 within the channel of the transistor.

The process flow described below beneficially provides source/drain (S/D) contacts that are self-aligned to the gate contact, and is compatible in every respect with a requirement to provide a high density layout.

In FIG. 1A the substrate 10 can be any suitable substrate, including a semiconductor substrate, a glass substrate, or a polymer-based substrate, that is compatible with the chemistries and temperatures used during the process flow. In the completed structure the substrate 10 is not electrically active. The insulating layer 12 can be any suitable electrically insulating material such as SiO₂. The CNT 14 can have a diameter in a range of, as non-limiting examples, about 0.5 nm to about 5 nm or greater, with a typical and suitable diameter being about 2 nm. The length of the CNT 14 can be any suitable value. In general a CNT can be characterized as having a length that greatly exceeds its width or diameter.

FIG. 1B shows the starting structure of FIG. 1A after the deposition of a non-damaging protective layer 16 over the CNT 14, followed by the deposition of a tri-layer resist stack composed of, for example, an organic planarization layer (OPL) 18, an oxide layer 20 and a resist layer 22. The non-damaging protective layer 16 can be formed by a spun-on-glass (SOG) process or by, for example, the atomic layer deposition (ALD) of SiO₂. In practice the thickness of the non-damaging protective layer 16 can be adjusted so that it completely embeds the CNT 14 with sufficient over-thickness to protect the CNT 14 during subsequent processing steps. The OPL 18 can be, for example, a resin applied by spin coating and baked to enhance structural integrity, or a liquid monomer applied by spin coating and hardened photochemically after an appropriate leveling period. In the practice of this invention any suitable OPL can be employed that is compatible with the ensuing processing steps. In general the OPL 18 is one that is preferably compatible with 400° C. processing, and the OPL 18 can have a thickness in a range of about 75 nm to about 400 nm or greater, with about 135 nm being a suitable value. The oxide layer 20 can have a thickness in a range of about 20 nm to about 35 nm and can be formed by a low temperature oxidation (LTO) process. The layer 20 can also be formed as a silicon-containing antireflection coating (SiARC). The resist layer 22 can have a thickness in a range of about 60 nm to several hundred nanometers, depending on the specifics of the photolithography process to be used during subsequent gate definition. In general the thickness of the resist layer 22 will be less than the thickness of the OPL 18.

FIG. 1C shows the structure of FIG. 1B after patterning of the resist layer 22 using, for example, e-beam lithography or optical lithography to form an opening 23 where the gate stack will be formed. After the opening 23 is formed in the resist layer 22 the underlying LTO or SiARC layer is patterned using a reactive ion etch (RIE) process that is selective to (i.e., stops on) the OPL 18. For example, a CF₄/CHF₃ RIE chemistry can be used. The resulting opening 23 through the resist layer 22 and the OPL or SiARC layer 20 can have a width in a range of, for example, about 5 nm to about 50 nm, or more preferably about 5 nm to about 20 nm. The width of the opening 23 defines the channel length of the transistor being fabricated.

FIG. 1D shows the structure of FIG. 1C after patterning of the OPL 18 using RIE, where the resist layer 22 is removed during the patterning process. The RIE process is selective to (stops on) the SiO₂ layer 16 in which the CNT 14 is embedded. For example, a CO₂/O₂ RIE chemistry can be used.

FIG. 1E shows the structure of FIG. 1D after a portion of the protective SiO₂ layer 16 is removed within the opening 23 using a dilute hydrofluoric acid (HF) solution etch to minimize isotropy. The result of the wet chemical etch is that the underlying portion of the CNT 14 is exposed. Note that the oxide layer 20 is also removed during the wet chemical etch. The wet chemical etch is preferred as the use of a dry etching process would have the potential to damage or degrade the CNT 14.

It can be noted that to achieve increased gate control and better electrostatics, a gate-all-around structure may be desired. To achieve a gate-all-around structure the insulator 12 can be selected such that it is also etched during the wet etch, or a separate wet etch may be used to remove portions of insulator 12 after insulator 16 is removed. The result is that the exposed portion of the CNT 14 is undercut and suspended above the surface of the substrate 10. Reference in this regard can be made to FIG. 1E′ that shows an undercut region 23A beneath the suspended CNT 14.

FIG. 1F shows the structure of FIG. 1E after gate stack deposition is performed. Preferably an ALD or a chemical vapor deposition (CVD) technique is used for the gate metallization step. If the CVD process is a plasma-enhanced CVD (PECVD) process then preferably O₂ is not present for the initial (gate dielectric) portion of the gate stack deposition, while if O₂ is present then a plasma-based process is avoided since the presence of free oxygen radicals can degrade or destroy the CNT 14 before it is passivated by another layer.

The gate stack metallization process proceeds by first blanket depositing a layer of gate dielectric 24 followed by a blanket deposition of desired gate metal (or metals) 26. The gate dielectric 24 can be any suitable dielectric material that will not be affected by subsequent processing steps. One suitable material is a high dielectric constant (high-k) material comprising a dielectric metal oxide having a dielectric constant that is greater than the dielectric constant of silicon nitride of 7.5. The high-k dielectric layer 24 may be formed by methods well known in the art including, for example, CVD and ALD. The dielectric metal oxide comprises a metal and oxygen, and optionally nitrogen and/or silicon. Exemplary high-k dielectric materials include HfO₂, ZrO₂, La₂O₃, Al₂O₃, TiO₂, SrTiO₃, LaAlO₃, Y₂O₃, HfO_(x)N_(y), ZrO_(x)N_(y), La₂O_(x)N_(y), Al₂O_(x)N_(y), TiO_(x)N_(y), SrTiO_(x)N_(y), LaAlO_(x)N_(y), Y₂O_(x)N_(y), a silicate thereof, and an alloy thereof. Each value of x is independently from 0.5 to 3 and each value of y is independently from 0 to 2. The thickness of the high-k dielectric layer 24 may be from about 1 nm to about 10 nm, and preferably from about 1.5 nm to about 3 nm. The gate metal layer 26 is deposited directly on the top surface of the high-k dielectric layer 24 and may be formed, for example, by chemical vapor deposition (CVD), physical vapor deposition (PVD), or atomic layer deposition (ALD). The material of the gate metal layer 26 may be, for example, a conductive transition metal nitride or a conductive transition metal carbide. Suitable materials include, but are not limited to, TiN, TiC, TaN, TaC, and a combination thereof. The gate metal layer 26 could also be composed of, as non-limiting examples, one or more of Au, Al, Pd and a Ni silicide.

At the completion of the processing steps shown in FIG. 1F the previously exposed portion of the CNT 14 (in FIG. 1E) is covered with the selected gate dielectric 24 that in turn is covered with the selected gate metal 26. This portion of the CNT 14 will function as the channel of the subsequently formed field effect transistor (FET).

For the embodiment of FIG. 1E′ the entire circumference of the CNT 14 is coated with the selected gate dielectric 24 and is surrounded by the selected gate metal 26, thereby providing the gate-all-around type of transistor structure.

FIG. 1G shows the structure of FIG. 1F after a RIE or a chemical mechanical polish (CMP) is used to remove the metal and dielectric in the field, stopping on the OPL 18. The process step basically planarizes the structure formed thus far.

FIG. 1H shows the structure of FIG. 1G after a re-application of LTO or SiARC material to form layer 28 and a second layer 30 of resist is deposited.

FIG. 1I shows the structure of FIG. 1H after a contact metal pattern is exposed as a shape that spans across the gate portion. An opening 25 is created by the selective removal of the resist layer 30. The width of the opening 25 is a function of the gate pitch (spacing between gates of adjacent devices). If a single device is being formed then the width may be about, for example, 50 nm.

FIG. 1J shows the structure of FIG. 1I after the LTO or SiARC material of the layer 28 is removed using RIE that is selective to the gate materials and the OPL 18. Exemplary and non-limiting RIE processes to perform this process step include the use of a fluorinated gas plasma, such as one employing CHF₃ and CF₄-based chemistries. At this point the opening 25 has been extended to the top surface of the OPL 18.

FIG. 1K shows the structure of FIG. 1J after the contact pattern is transferred into the OPL 18 using a RIE process that is selective to the gate stack. Exemplary RIE chemistries that are suitable for use during this processing step include O₂, H₂ and NH₃ based plasmas.

FIG. 1L shows the structure of FIG. 1K after the protective SiO₂ layer 16 is removed using a dilute HF solution within the opening 25 that defines the contact pattern. The high-k dielectric layer 24, metal gate electrode 26 and the OPL 18 materials are not affected by the HF etch. For better contact to the CNT 14 a wrap-around contact may be desired. To achieve a wrap-around contact, insulator 12 may be selected such that it is also etched during the wet etch, or a separate wet etch may be used to remove portions of insulator 12 after insulator 16 is removed. Note that the wrap-around contact may be used in conjunction with the wrap-around gate processing step shown in FIG. 1E′, or it may be used without the wrap-around gate processing step shown in FIG. 1E′.

FIG. 1M shows the structure of FIG. 1L after the desired source (S) and drain (D) contact material 32 is deposited adjacent to the gate (G) stack using, for example, ALD or CVD processes and then subsequently etched back using RIE selective to the OPL 16. The contact metal 32 can be applied by a thermal evaporation process, or by a plating process if the contact metal is, for example, Cu. The contact metal that is used can depend on whether an nFET or a pFET is being formed. For an nFET a lower work function (WF) metal system such as Ag or Al can be used, while for a pFET a higher WF metal system such as Au or Pd can be used. Those portions of the CNT 14 that are exposed during the processing step shown in FIG. 1L are over-coated with and electrically conductively coupled to the applied contact metal. 32.

FIG. 2 is an enlarged sectional view, also not drawn to scale, through the structure at the completion of the processing of FIG. 1M (along a plane indicated as ‘2’ in FIG. 1M). The sectional view is taken through the gate stack and shows the CNT 14 supported by the insulator layer 12 and covered with gate insulator 24 (e.g., the high-k gate insulator material) beneath the gate metal 26. The gate stack and contact metal are embedded in the surrounding protective SiO₂ layer 16 and the OPL 18.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

The corresponding structures, materials, feature dimensions, layer thicknesses, layer materials, etchants and etching processes, and equivalents of all means or step plus function elements in the claims below are intended to include any structure, material, or act for performing the function in combination with other claimed elements as specifically claimed. The description of the present invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.

As such, various modifications and adaptations may become apparent to those skilled in the relevant arts in view of the foregoing description, when read in conjunction with the accompanying drawings and the appended claims. As but some examples, the use of other similar or equivalent mathematical expressions may be used by those skilled in the art. However, all such and similar modifications of the teachings of this invention will still fall within the scope of this invention. 

What is claimed is:
 1. A method of forming a field effect transistor, comprising: providing a substrate having a carbon nanotube disposed over a surface of the substrate; forming a protective electrically insulating layer over the carbon nanotube; forming a first multi-layer resist stack over the protective electrically insulating layer, the first multi-layer resist stack comprising a bottom layer, an intermediate layer and a top layer of resist; patterning and selectively removing a portion of the first multi-layer resist stack to define an opening for a gate stack, where selectively removing also completely removes the intermediate layer and the top layer of resist leaving the bottom layer; selectively removing a portion of the protective electrically insulating layer within the opening to expose a first portion of the carbon nanotube; forming the gate stack within the opening and upon the exposed first portion of the carbon nanotube; forming a second multi-layered resist stack upon the bottom layer and upon the gate stack; patterning and selectively removing a portion of the second multi-layer resist stack to define an opening for a source contact and an opening for a drain contact; selectively removing a portion of the protective electrically insulating layer within the source contact opening and within the drain contact opening to expose a second portion of the carbon nanotube and a third portion of the carbon nanotube; and applying contact material within the source contact opening and within the drain contact opening and upon the exposed second and third portions of the carbon nanotube.
 2. The method of claim 1, where forming the gate stack comprises forming a layer of gate insulator that is disposed upon the exposed first portion of the carbon nanotube followed by a layer of gate metal that is disposed upon the layer of gate insulator.
 3. The method of claim 2, where the layer of gate insulator is comprised of a high dielectric constant material.
 4. The method of claim 1, where forming the protective electrically insulating layer over the carbon nanotube comprises one of using spin-on-glass or atomic layer deposition of SiO₂.
 5. The method of claim 1, where forming the first multi-layer resist stack forms the bottom layer to be an organic planarization layer and the intermediate layer to be a low temperature oxide layer or a silicon-containing antireflection coating.
 6. The method of claim 1, where selectively removing a portion of the first multi-layer resist stack comprises performing a first reactive ion etch process to initially form the opening through the resist layer and the intermediate layer, a performing a second reactive ion etch process to complete forming the opening through the bottom layer so as to expose the protective electrically insulating layer within the opening.
 7. The method of claim 1, where selectively removing the portion of the protective electrically insulating layer within the opening to expose the first portion of the carbon nanotube uses a wet chemical etch process.
 8. The method of claim 7, where the protective electrically insulating layer is comprised of SiO₂, and where the wet chemical etch process uses HF.
 9. The method of claim 1, where selectively removing the portion of the second multi-layer resist stack uses a reactive ion etch process that is selective to the gate stack and the bottom layer.
 10. The method of claim 9, where the bottom layer is formed as an organic planarization layer, and where the reactive ion etch process uses a fluorinated gas plasma.
 11. The method of claim 1, where the method simultaneously forms a plurality of gate stacks and associated source and drain contacts disposed along a length of the carbon nanotube.
 12. The method of claim 1, where there are a plurality of carbon nanotubes each having the first portion passing through the gate stack and defining a channel.
 13. The method of claim 1, where the contact material is comprised of a metal having a work function selected for forming one of an nFET or a pFET.
 14. The method of claim 1, where selectively removing the portion of the protective electrically insulating layer within the opening to expose the first portion of the carbon nanotube exposes the entire circumference of the carbon nanotube such that the exposed portion of the carbon nanotube is suspended above the surface of the substrate.
 15. The method of claim 1, where selectively removing the portion of the protective electrically insulating layer within the source contact opening and within the drain contact opening to expose the second portion of the carbon nanotube and the third portion of the carbon nanotube exposes the entire circumference of the second portion and the third portion of the carbon nanotube such that the exposed second and third portions of the carbon nanotube are suspended above the surface of the substrate. 